Dehydration products of pine oil and process of producing same



Patented Nov; 13,'l 928. I

UNITEDST'ATES P ATENT OFFICEQ mm W. Emmy, or wmron,

NEW JERSEY, ASSIGNOR T HERCULES POWDER comm, or wrnume'ron, nnnawnnn', A CORPORATION or DELAWARE. I

' Damnation mews or rmn' 011. AND raoc'nss or PRODUCING emu.

Io mum,

I 'n'the processes for the extraction of resin from resinous wood, there are also recovered substantial quantities of pine 011 and turpentine. Since turpentine is usually more val- 5 uable thanine oil, and since other operations carrie on by the producer may require the use of larger quantities of turpentine, for solvent or other purposes, than is produced in the wood extractingprocess, there may be no use, or but a limited use, for pineoil; or, due to temporary market conditions, there may be little demand for pine oil and a big a demand for turpentine. I have discovered that pine oil may be converted into a substance that may be used, for most or all purses, as a substitute for turpentine, and that as, m general, solvent properties superior to those of turpentine, although inferior to those of pine o 1 I have also discovered that my process ma be so'carried out as to produce a limited; but substantial, amount of other products,particularl A borneol, which may have, as borneol has, aliigher value perlunit weight than either pineoil, or the turpentine sub qstitute, or turpentine. v

I My 'rocess comprises the dehydration of pine oi The preferred method of executing my process involves the addition of the halogen to the pine -oil, followed by slow distillation, preferably (but-not necessaril with the introduction of the disti ate being the tur ntine substitute above mentioned. The 'alo'gens that I have found most efiective'as dehydrating ents are iodin, chlorin and bromin, but 'io im is preferred. Deh dration witha halogen is carried out,

re erably,by addition of the halogen, folowed by distillation as 40 it is also possible to add the halogen and then I reflux for a-time. Theadvanta e-of the use 7 of a halogen is that the-high boiling residue contains a greater proportion of the more valuable constituents thanisobtained b the use of any other dehydrating agent, wit the 'powble exception of argallaceous. earths, such as fuller s earth, or of silicious earths such askieselguhr, or'of activated carbon. \Probably'the'most valuable-of these constit-- uents is borneol. -Iodin "vesthe maximum possible amount of selective dehydration between the tertiary and secondary alcohols, i. o it yields a residue containing a greater I Application med July 20,

present. In addition,

above stated but but from five to 'redistillor to make's'evera 1926. Serial No. 123,818.

proportion of borneol and fenchyl alcohol J than can be obtained by using other reagents. In view, therefore, of the peculiar utility of a halogen as a dehydrating agent for pine oil, I have claimed it herein specifically and do not intend to cover the other dehydrating agents herein specified, which are made the subjectpf aiseparate application filedof even date herewith, Serial N 0. 123,814, filed July 20,1926, 7 I a The chief ,constituent of pine oil is alpha-- terpineol, bu't' considerable amounts of other, oxygenated bodies, as well as a small proportion of'terpene hydrocarbons, are also present The dehydrating agent splits ofl chemically combined water, forming tenpene hydrocarbons that are isomeric with pinene. The main reaction may be represented thus:

m n m m H,2O

Di ntene is the most important hydrocarbon t at is formed, but other terpene hydro- I5 carbons, such as terpinene and limonene, are.

small amounts of par- ;aflin and aromatic hydrocarbons may be formed in certain cases.

As above stated, the halogen is added to the pine oil, and the hydrocarbons are then slowly distilled oif through a fractionating column substantially as rapidly as they areformed. I In case the halogen chosen is chlorin or bromin, it may be desirable to dissolve the halogen in a small amount of an inert solvent, such as carbon tetrachloride, previous to adding it tothe pine oil. Dehy- 3 dration occurs more readily with iodin'than v with any of the other halo ens. From sixty to eighty-five" er-cent of t e pine oil is distilled over. T e distillate consists chiefly of the terpene hydrocarbons above mentioned, to twenty-five per cent of pine oil is also present therein. T The density, boiling range, and percentage of the distillate vary somewhat according to operating conditions. It ma be desirable I cuts-inthe' distillate, and it, is desirable to give the distillate an alkali wash. a In general, it may be stated that the specificgravity of the distillate at 15C. is within theagproximaterange 85to .89, I from 'si'xtyve to ninety five per cent distil- 1e, ling ofi below C.

ioo

I gen usuali gives neol. Additional The high boiling residue amounts to irom ten to thirty-five percent of the original within the approximate range .94 to .99. it consists essentially of various constituents of the pine oil that ha've not been converted into the product above. described, which I designate solvenol. The residue is adapted for use as an ingredient of disinfectants. Some of the constituentsoi the residue are more valuable than either pine oil, solvenol or turpentine- One of these more valuable constituents is borneol. Of these valuable constituents, borneol, at least, is not present in substantialproportion unless a mild dehydrating agent, such as a halogen of fullers earth, is employed and of'these two agents, the halothe larger yleld. The borneol ma partially recovered b cooling the resi' he, with crystallization o the bor borneol may be recovered by fractionation of the residue, followed by cooling of the fractions.

The halogen used as the dehydrating agent should be added to the pine 011 in a proportion varying from .05 to 1.0 percent. About 0.1% is usually preferred.

It will now be observed that by virtue of my inventionnot only is an eflicient and eco-v nomical method for the roduction of a turntine substitute p'rovi ed, but in addition rneol is produced in substantial proportion.

Having now full described my invention, what I c aim and eclare to protect by .Letters Patentis:

1'. The-process of producingl a turpentine substitute from pine oil'whic hydrating the pine oil with a halogen. 2. The process of securing. a turpentine substitute and borneol from pine oil which includes adding a halogen to the pine-oil,

distilling Oct substitute ing a halogen to pine oil anddistilling ofi' includes dehydrocarbons comprising {he turpentine substitute, and separating the orneol from the, residue. I

3. The process of producing a turpentine substitute from pine oil which includes adding to thepine oilfrom not lessthan .05 per cent of iodin and distilling.

4. The process 0 a halogen, distilling ofi a arating the borneol from the residue 5. As a new article of manufacture, a

neutral residual product of the dehydration, having a specific gravity, at a temperature of -C.,within of pine oil in liquid phase,

the approximate range .94 to .99.

, 6. As a new article of manufacture, a neutral residual product of the dehydration of pineoil in liquid phase with iodin, having a specific gravity, at .a temperature of-15 C.,'within the approximate range .94 to .99

containing a substantial proportion of borneol and which on distillation will produce a substantially neutral distillate.

f securing borneol from pine oil which includes adding turpentine substitute and sep- 7. The process of producing a turpentine substitute from pine oil which includes sub- ]ecting pine 'oil to treatment with a halogen and heat..

,8. The process of p J roducing a tur entine substitute from pine oil which inclu es'subilectting pine oil to treatment with iodin and 9. The process ofproducing. a turpentine from pine oil which includes add the tur entin'e substitute.

- 10.; T e roce'ss of producing a turpentine substitute om pine oil which includes addturpentine s11 fstitute.

In testimony of which invention I have hereunto set my'hand at Kenvil," J on this 26th d'a'y of June, 1926.

ing iodin to ine oil and distilling off the 

